Cu/Ce负载对赤泥脱除中低温烟气中NO的促进作用

李扬; 徐博; 杨赫; 靳立军; 胡浩权

doi:10.1016/S1872-5813(23)60388-3

Cu/Ce负载对赤泥脱除中低温烟气中NO的促进作用

doi: 10.1016/S1872-5813(23)60388-3

大连理工大学化工学院煤化工研究设计所精细化工国家重点实验室辽宁大连 116024

基金项目: 国家重点研发计划(2018YFB0605104), 国家自然科学基金(22278066)和中央高校基本科研业务费(DUT2021TB03)资助

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Tel: 0411-84986157，E-mail: hhu@dlut.edu.cn

中图分类号: X511
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出版历程
- 收稿日期: 2023-05-04
- 修回日期: 2023-06-24
- 录用日期: 2023-06-25
- 网络出版日期: 2023-10-31
- 刊出日期: 2024-03-10

Promotion of Cu/Ce supported red mud for NO removal from low and medium temperature flue gas

State Key Laboratory of Fine Chemicals, Institute of Coal Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

Funds: The project was supported by National Key R&D Program of China (2018YFB0605104), National Natural Science Foundation of China (22278066) and The Fundamental Research Funds for the Central Universities (DUT2021TB03)

摘要

摘要: 本研究对酸洗赤泥催化剂进行Cu、Ce、Cu/Ce浸渍负载，并研究了金属改性赤泥对烟气中NO_x的催化转化性能。研究结果表明，Cu负载催化剂中的Cu⁺与Cu²⁺，有效促进了赤泥对低温烟气(200–300 ℃)中的NO转化率，Cu的负载量达到6%时，赤泥的最高NO转化率达到了90.7%；而Ce负载催化剂中的Ce³⁺与Ce⁴⁺，有效促进了赤泥对中温烟气(200–400 ℃)中的NO转化率，Ce的负载量达到8%时，赤泥的最高NO转化率达到了94.0%；Cu/Ce负载催化剂表现出比单金属负载催化剂更好的低温NO转化率，最佳的负载Cu:Ce比例为1∶1，双金属负载催化剂表现出比Cu负载催化剂更好的中温(300–400 ℃)中的NO转化率，最高达到了95.5%。其原因是，在Cu/Ce协同作用下，Cu⁺以及Cu²⁺的还原过程分别从229、302 ℃降至201以及247 ℃，同时使发生Fe₂O₃→FeO的还原过程的温度降低，促使ACRM-Cu1Ce1具有更强的低温氧化还原能力，同时，双金属负载使催化剂具有更高的弱酸性峰，也使催化剂的强、弱酸性峰都向低温偏移，并使负载后的赤泥具有了较高的Fe离子平均氧化态以及较高的Cu⁺含量，促进了赤泥催化剂对低温NO的转化率。
- 赤泥 /
- SCR /
- Cu /
- Ce /
- 负载
Abstract: Red mud is a solid waste in aluminum industry and has been proven to be an efficient alternative to NO_x selective catalytic reduction (SCR) catalysts. Acid washing treatment to red mud can improve its alkalinity and surface properties, and increase the conversion rate of NO_x. In this paper, Cu, Ce, and Cu/Ce was supported on acid washed red mud and NO_x catalytic conversion performance on metal modified red mud catalysts was studied. The research results indicate that Cu⁺ and Cu²⁺ in the Cu supported catalyst effectively promote NO conversion rate of red mud in low-temperature (200−300 ℃) flue gas, reaching a maximum of 90.7%; Ce³⁺ and Ce⁴⁺ in Ce supported catalysts effectively promote the NO conversion rate of red mud in flue gas at 200–400 ℃, reaching a maximum of 94.0%; Cu/Ce supporting exhibits better NO conversion rate than single metal supported catalysts at low-temperatures, the optimal Cu∶Ce ratio for supporting is 1∶1; and also exhibits better NO conversion rate than Cu supported catalysts at high-temperature (300−400 ℃), reaching a maximum of 95.5%. The reason may be that under the synergistic effect of Cu/Ce, ACRM-Cu1Ce1 has stronger low-temperature redox ability, higher weak acidic peaks, higher average oxidation state of Fe ions, and higher Cu⁺ content.
- red mud /
- SCR /
- Cu /
- Ce /
- supporting

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FIG. 3015. FIG. 3015.

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图 1 实验装置流程示意图

Figure 1 Schematic diagram of experimental apparatus

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图 2 Cu负载量对催化剂NO转化率的影响(BFG)

Figure 2 The effect of Cu supporting on the NO conversion rate of catalysts (BFG)

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图 3 Ce负载量对催化剂NO转化率的影响(BFG)

Figure 3 The effect of Ce supporting on the NO conversion rate of catalysts (BFG)

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图 4 Cu/Ce负载比例对催化剂NO转化率的影响(BFG)

Figure 4 The effect of Cu/Ce supporting ratio on the NO conversion rate of catalysts (BFG)

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图 5 不同催化剂的NO转化率(BFG)

Figure 5 NO conversion rate of different catalysts (BFG)

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图 6 负载金属催化剂的等温吸附曲线与孔径分布

Figure 6 Isothermal adsorption curves and pore size distribution of the supported catalysts

(a), (b) and (c) are the isothermal adsorption curves of Cu supported, Ce supported and Cu/Ce supported catalysts, respectively; (d), (e) and (f) are the pore size distribution of the corresponding catalysts.

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图 7 负载催化剂的XRD谱图

Figure 7 XRD patterns of supported catalysts

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图 8 负载催化剂的H₂-TPR谱图

Figure 8 H₂-TPR profiles of supported catalysts

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图 9 负载催化剂的NH₃-TPD谱图

Figure 9 NH₃-TPR prefiles of supported catalysts

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图 10 负载催化剂的Fe 2p谱图

Figure 10 Fe 2p spectra of supported catalysts

(a): ACRM; (b): ACRM-Cu6; (c): ACRM-Ce8; (d): ACRM-Cu1Ce1.

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图 11 金属负载催化剂的Cu 2p谱图

Figure 11 Cu 2p spectra of supported catalyst

(a): ACRM-Cu6; (b): ACRM-Cu1Ce1.

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图 12 金属负载催化剂的Ce 3d谱图

Figure 12 Ce 3d spectra of supported catalysts

(a): ACRM-Ce8; (b): ACRM-Cu1Ce1.

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图 13 负载催化剂的O 1s谱图

Figure 13 O 1s spectra of supported catalysts

(a): ACRM; (b): ACRM-Cu6; (c): ACRM-Ce8; (d): ACRM-Cu1Ce1.

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表 1 赤泥的组成分析

Table 1 Analysis of the composition of red mud

Sample	Fe₂O₃	Al₂O₃	SiO₂	TiO₂	Na₂O	Others
RM/%	42.0	21.3	22.5	3.7	6.9	3.6

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表 2 催化剂的比表面积与孔径分布

Table 2 Surface area and pore size distribution of catalysts

Sample	S_BET/(m²·g⁻¹)	v_t/(cm³·g⁻¹)	d_ave/nm
ACRM-Cu1	51	0.155	9.3
ACRM-Cu2	53	0.168	9.8
ACRM-Cu4	45	0.149	9.7
ACRM-Cu6	44	0.156	10.3
ACRM-Cu8	42	0.149	14.2
ACRM-Ce1	50	0.172	9.8
ACRM-Ce2	54	0.162	9.6
ACRM-Ce4	49	0.148	9.4
ACRM-Ce6	49	0.147	9.6
ACRM-Ce8	50	0.137	9.2
ACRM-Cu3Ce1	42	0.146	10.7
ACRM-Cu2Ce1	41	0.154	11.5
ACRM-Cu1Ce1	43	0.137	10.1
ACRM-Cu1Ce2	45	0.139	10.0
ACRM-Cu1Ce3	48	0.143	9.4

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